Diazine-aldehyde resinous condensation products



Patented Aug. 13, 1940 UNITED STATES DIAZlNE-ALDEHYDE RESINOUS CON-DENSATION PRODUCTS Werner Zerweck and Karl Keller, Frankfort-onthe MainFechenheim, Germany,

assignors to I. G. Farbenindustrie Aktiengesellschaft,Frankfort-on-the-Main, Germany No Drawing. Application September 24,1938,

Serial No. 1936 4 Claims.

Our U. S. application Serial No. 124,034, flied February 4, 1937,relates to resinous condensation products and process of making same.

Our present invention is a continuation in part 5 of the saidapplication and relates to resinous condensation products and process ofmaking same more particularly to those obtained by condensing a lowaliphatic aldehyde containing a chain of at the most 4 carbon atoms,particularly l0 formaldehyde or other compounds splitting off aldehydeswith compounds of the general formula:

c- (NHX).

N wherein n is at least 2, X stands for a member so of the groupconsisting of H and NH2 and wherein to the carbon atoms, radicles of thegroup 'consisting of the aforesaid NHX-groups, hydrogen,

alkyl, phenyl, phenylene, hydroxy, alkoxy, mercapto, thioether andsubstituted amino groups are 25 attached.

As suitable compounds are to be named amino-,

hydrazinoand aminohydrazino compounds of the pyrimidine, quinazoline andquinoxaline series which may contain further substituents of the 30aforesaid type.

One molecular weight of the above compound is treated with at least onemolecular weight of the aldehyde. The condensation may be carried out inneutral, acid or alkaline condition, in the cold or in the hot and inorganic or inorganic liquids or molten masses. Further on thecondensation may be performed without additions of other substances andthe condensation products thusobtained may be mixed with fillingmaterials and dyestuifs, or the condensation may be carried out in thepresence of fillers and dyestuffs. The condensation is accelerated bythe addition of acids or acid-forming compounds, whereas it is retardedby the addition of alkalies and organic bases.

Beside the above compound there may be added to the condensation mixtureother compounds which are capable of condensing with aldehydes such forexample as urea, thiourea, substituted 0 ureas, polymethylene-ureas,dicyandiamide, guanidine, sugars of all kinds, sulphonamides, monoorpolycarboxylic acid amides, aminobenzenes, phenols etc. However, theamount of the above compound employed should not be too small; it mustbe the main ingredient of the total quantity In Germany June 24,

of the compounds which are capable of condensmg with the aldehyde inorder to give prominence to the valuable properties of the abovecondensation product. The resins thus obtained may be employed inadmixture with other natural or artificial resins such for example asphenol, urea, aniline, alkyl and ketone resins.

The present condensation products are singularly valuable substancesbecause they combine the good properties of electric insulation and highresistance to water of the known aniline-formaldehyde resins with thecolorlessness and resistance to light of the urea resins. They may beheated to 200 and more without decomposition, they are very resistanteven to boiling water and hot water vapour and they are colorless andstable to light. They are particularly suitable for the manufacture ofmoulded articles because in the hot moulding press they pass overquickly into their final state. They are therefore particularly adaptedfor the manufacture of gramophone records. Just as with the knownhardening artificial resins the new products can be worked up withvarious kinds of fillers and dyestuffs, and they show great stabilityand resistance to heat and light, even when employed with organicfillers. The finished moulded articles are distinguished by absence ofscent and taste. For being employed for electrical engineering they havethe advantage of a very good insulating power and othergood electricproperties, particularly a good resistance to surface leakage'current.They are ,therefore especially adapted for the manufacture of objects ofelectric insulation and construction, which are often or for a long timeexposed to temperatures of 100 and more, such as parts ofswitches,lamp-pedestals and 1amp-shades, contacts of flatirons, bearing-dishes,particularly of boxes for wireless apparatus, moreover for themanufacture of vessels and utensils which are often orfor a long timeexposed to aqueous liquors, such as cups, bowls, cans, boxes,particularly for soap buttons, vases, domestic utensils of various kind,medical and sanitary articles, sets of teeth, coatings for tables andpieces of furniture and the like. Moreover they may be used as fireprotecting agents, particularly when a sugar has been added during orafter the condensation reaction.

When the new resins are employed as lacquers and impregnating agents,coatings resistant to water and light are formed in a short time with orwithout heating. Moreover the new resins are suitable for gluing andcementing of various articles.

In order to further illustrate our invention the following examples aregiven, the parts being by weight and all temperatures in degreescentigrade.

Example 1 12.5 parts of 2,4,6-triaminopyrimidine of the formula:

are dissolved in about 30 parts of formaldehyde of 30% strength. Thesolution is heated for some time and then evaporated at about 100. Byfurther heating hardening occurs. A transparent well lustrous waterinsoluble product is obtained. Example 2 16 parts of2.4-diaminoquinazoline of the formula:

ate by adding an inorganic or organic base such as pyridine to thesolution and then evaporating the solution, after hardening a verylustrous condensation product particularly repelling water is obtained.

Example 3 15 parts of 2,4,5,6-tetraaminopyrimidine of the formula:

HrN-C If HzN-C C-NH:

N are dissolved by warming in about 40 parts of formaldehyde of 30%strength. The solution is held for some time at about 60, thenevaporated and the residual resin is heated for some hours at about 100to 120 until hardening has occurred. The product thus obtained is verywaterproof.

Example 4 16 parts of 6-hydroxy-2.4-diaminopyrimidine of the formula:

are finely powdered and intimately mixed with about 10 parts ofparaformaldehyde. The powder obtained is exposed for some hours to aheating under pressure at about 100 to 120. A hard and waterproofpressed product is obtained,

Example 5 25 parts of a condensation product (obtained by condensingcyandesoxybenzoine with guanidine) of the probable formula:

which forms white crystals melting at 220 to 221, are dissolved in about20 parts of water and 60 parts of formaldehyde of 30% strength whilewarming. Then the water is removed by evaporation and the residual softresin is heated at 80 to for some hours. In this manner a hard whitecondensation product is obtained, which is still soluble in boilingwater. By heating it for a longer time at temperatures above it isconverted into the water insoluble state while splitting offformaldehyde.

When replacing the above diphenyldiaminopyrimidine by a correspondingamount of 6- phenyl-2.4-diamino-pyrimldine of the formula:

u T o a...

likewise a resinous hard condensation product is obtained which morerapidly is hardened and converted into the water-insoluble state.

Example 6 10 parts of 5,6-benzo-2,4-diamnoquinazoline of the formula:

a BN

1 2( NHr N of 198 melting point obtainable for instance by acting athigher temperatures with alcoholic ammonia on5,6-benzo-2A-dichloroquinazoline (which latter compound may be preparedby the action of a mixture of phosphorus pentachloride and phosphorusoxychloride on 5,6-benz0-2,4- dioxoquinazoline) are mixed with an excessof a formaldehyde solution of 30% strength and 1 part of pyridine andthe mixture is warmed at about 60 to 70 whereby rapidly a clear solutionoccurs. The solution is evaporated in vacuo and the residue is heatedfor some hours at 100 to whereby a light water insoluble resin isformed.

Example 7 A mixture of 60 parts of 2,4,6-triaminopyrimidine, 95 parts ofphenol, 250 parts of formaldehyde of 30% strength and 1 part of sodiumhydroxide is heated at about 80 until the formation of resin occurs.Then the formed resin is milled with 200 parts of wood powder and dried.From'such a molding mass articles of a good resistance towards light andwater can be made.

Instead of the said quantity of formaldehyde one may use about 80 partsof acetaldehyde with the addition of the corresponding amount of water.

Example 8 A mixture of 60 parts of urea and about 200 parts of aneutralized formaldehyde solution of 30% strength is heated to boilingfor about 3 hours. When cool 30 parts of 2,4,6-triaminopyrimidine andparts of cellulose are added. After drying and comminuting a mouldingpowder is obtained which can be used for the manufacture of articles bymeans of pressure and heat, which articles exhibit a greater resistanceto water than those prepared from-resins obtained without the additionof triaminopyrimidine.

A similar product is obtained when replacing urea by the correspondingamount of thiourea.

Example 9 parts of 2,4,6-triaminopyrimidine, parts of propylaldehyde and100 parts of wood powder is mixed for about an hour at about 50 in aknead apparatus. After drying for about 2 hours at about 60,advantageously in vacuo a valuable moulding mass is obtained.

One may replace the propylaldehyde by butyraldehyde.

Example 10 dried in the heat can be moulded to plates and the like.

Example 11 In a kneading apparatus, which is heated at about 50, forabout 2 hours 80 parts of 2,4,6-triaminopyrimidine are milled with 50parts of glycerol, parts of formaldehyde of 30% strength and 200 partsof cellulose. The formed homogeneous and moist mass. is dried. Bycomminuting in a mill, in a given case with the addition of dyestuffsand melting agents a moulding powder is obtained, which can be rapidlytransformed into hard and solid articles under pressure at temperaturesranging from 120 to Instead of glycerol other fillers such as starch,glucose, cane sugar and the like can be added.

' Example 12 A mixture of 100 parts of 2,4,6-triaminopyrimidine, 15parts of dicyandiamide, 50 parts of glucose, 1 part of sodium carbonateand 280 parts of formaldehyde of 30% strength is stirred while warmuntil total solution. With a such solution sheets of 'paper areimpregnated, which after drying are pressed in the heat to plates.

Example 13 15 parts of 2-mercapto-4,6-diaminopyrimidine of the formula:

ll HaN-C are stirred with a little amount of water while forming a thinpulp and then warmed with the addition of 60 parts of formaldehyde of30% strength and about 3 to 5 parts of pyridine, until the mass has beendissolved. Then the water is distilled 011 and the residual resin isheated for some time at temperatures a little higher than 100. In thismanner a hard and very water-proof resin is obtained.

A similar product is obtained by starting from2-hydroxy-4,6-diaminopyrimidine of the formula:

Example 14 When starting from 2-methylthio-4,6-diaminopyrimidine of theformula:

a resin is obtained which is very waterproof and particularly resistantto the action of alkaline liquors.

Example 15 32 parts of 2-cyanamino-4,6-diamino-pyrimidine of theformula:

a m \N HINC are stirred with a little amount of water and heated afterthe addition of about 100 parts of formaldehyde of 30% strength until aclear solution occurs. Then the solution is evaporated and the residueis hardened at about 120. The resin thus obtained is very waterproof.

Example 16 17 parts of 2,6-dihydroxy-4,5-diamino-pyrimidine of theformula:

Example 17 20 parts of 2-phenyl-4,6-diamino-pyrimidine of the formula:

are heated at about 90 for some time after;-th

addition of about 60 parts of formaldehyde of 30% strength. Whensolution has occurred it is held for 1 to 2 hours at 50 to 60 and thenit is evaporated in vacuo. The residual resin is heated for some hoursat about to The formed product is a very solid mass which is resistantto heat, to water and to the action of acids and alkalies.

Example 18 63 parts of 2-hydroxy-4,6-diaminopyrimidine are milled in aknead apparatus with 60 parts of propylaldehyde and 50 parts of woodpowder for about an hour at 50 to 60. The formed mass is intimatelymixed with 100 parts of a commercial moulding powder based on urearesins, such as Pollopas. Articles obtained from such a mixture areessentially more resistant to water than the Pollopas articlesthemselves.

Example 20 In a kneading apparatus, which is heated at about 50, forabout 3 hours 50 parts of Z-methylthio-4,6-diaminopyrimidine are milledwith 25 parts of glycerol, 100 parts of formaldehyde of 30% strength and100 parts of cellulose. The formed homogeneous and moist mass is dried.By comminuting in a mill, in a given case with the addition of dyestuffsand melting agents a moulding powder is obtained, which can be rapidlytransformed into hard and solid articles under pressure at temperaturesranging fromlOO to 150. Instead of glycerol other fillers such asstarch, glucose, cane sugar and the like can be added.

Example 21 15 parts of 2,4,6-trihydrazido-pyrimidine of the formula:

obtained by acting with hydrazine on 2,4,6-tri amino-pyrimidine, arestirred with some water to a thin paste, then about 2 parts of pyridineand at 60 to 70 about 50 parts of formaldehyde of 30% strength are addedand the mixture is heated until total solution. Then the solution isevaporated in vacuo and the residual resin is hardened at temperaturesabove 100. A very waterproof and hard polymerization product is obtaind.

A similar resin is obtained when startingv from2,4-dihydrazidoquinazoline of the formula:

"" N H-NH:

obtainable by acting with hydrazine on 2,4-dichloro-quinazoline.

Example 22 20 parts of 2-hydroxy-4,6-dihydrazido-pyrimidine of theformula:

NIH-NH:

HzN-HN-g (B-QH obtainable by acting with hydrazine hydrate on2-hydroxy-4,6-diamino-pyrimidine are mixed with 2 to 3 parts ofpyridine, about 25 parts of water and about 60 parts of formaldehyde of30% strength are heated until the mass has been dissolved. The water isremoved by evaporation and the residual resin is heated for some time attemperatures above 100. A hard and very waterproof product is thusobtained.

Ezample 23 A mixture of 40 parts of aminohydrazinoquinazoline of theformula:

of 229 to 230 melting point, obtained by acting at 10 to 20 withconcentrated ammonia on 2,4- dichloroquinazoline and subsequentlydecomposing at about 80-490 the formed monochloromonoaminoquinazoline of235 melting point with hydrazine hydrate, 35 to 70 parts of formaldehydeof 40% strength, 10 to 15 parts of pyridine and a little quantity ofwater is heated for some time until solution occurs. The solution isevaporated in vacuo and the remaining resin is heated for some timeattemperatures above 100. According to the amount of the formaldehyde usedand the temperature and duration of the heating process resins areobtained, which are to a more or less degree plastic in the heat. Atroom temperature they are hard and have a good resistance to water.

Example 24 Example 25 10 parts of 5,6-benzo-2.4-dihydrazinoquinazolineof the formula:

NH-NHI obtainable for instance by acting at higher temperatures withhydrazine hydrate on 5,6-benzo- 2,4-dichloroquinazoline, are mixed withan excess of formaldehyde of 30% strength and 1 part of pyridine and themixture is warmed at about 60 to 70. Thereby rapidly a clear solutionooours. The solution is evaporated in vacuo and the residue is heatedfor some hours at 100 to 110, whereby a light waterinsoluble resin isformed. 1

We claim: 7 v

1. Resinous condensation products obtained by condensing a low aliphaticaldehyde containing a chain of at the most 4 carbon atoms with acompound of the general formula:

- (N'flX).

wherein n is at least 2, X stands for a member of the group consistingof H and NH: and wherein to the carbon atoms, radicles of the groupconsisting of the aforesaid NHX-groups, hydrogen, alkyl, phenyl,phenylene, hydroxy, alkoxy, mercapto, thioether and substituted aminogroups are attached.

2. A resinous condensation product obtained by condensing2,4,6-triamino-pyrimidine of the formula:

with formalehyde Lmtil the formation of the resin, which condensationproduct is transparent well lustrous and characetrized by good electricproperties, resistance to water, heat and light, by colorlessness, whichproduct is adapted for the use as lacquers, gluing agents and for themanufacture of pressed articles.

3. A resinous condensation product obtained by condensing2,4-diamino-quinazoline of the formula:

( l-NH:

V with formalehyde until the formation of the resin, which condensationproduct is a very lustrous product particularly repelling water andcharacterized by good electric properties, resistance to water, heat andlight, by colorlessness, which product is adapted for the use aslacquers, gluing agents and for the manufacture of pressed articles.

4. A resinous condensation product obtained by condensing 2mercapto-4,6-diamino-pyrimidine of the formula:

with formaldehyde until the formation of the resin, which condensationproduct is a hard and very waterproof resin and characterized by goodelectric properties, resistance to water, heat and light, bycolorlessness, which product is adapted for the use as lacquers, gluingagents and for the manufacture of pressed articles.

' WERNER ZERWECK.

